Powder dispersant for hydraulic compositions

ABSTRACT

The present invention provides a powdery dispersant for hydraulic compositions, which is excellent in pumping before drying and in pressure resistance and humidity resistance, which comprises one or more copolymers obtained by polymerizing a specific vinyl monomer (a) such as an ethylenically unsaturated carboxylic acid derivative having a polyoxyalkylene group with a specific vinyl monomer (b) such as (meth)acrylic acid etc., wherein the average number of C 2-4  oxyalkylene groups or oxystyrene groups added is 45 to 150, (a)/[(a)+(b)]×100 ranges from 15 to 45 (mole-%), and at least a part of the copolymers are monovalent or polyvalent metal salts.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a powdery dispersant forhydraulic compounds such as cement, gypsum etc., particularly for use ingrout mortar and to a hydraulic composition comprising the same.

[0003] 2. Description of the Prior Art

[0004] As a dispersant for hydraulic compounds, a monovalent metal saltof a polycarboxylic acid-based copolymer has been used usually as aliquid product because of its high dispersibility. For furtherimprovement of convenience, the metal salt is formed into a powderydispersant, and a product comprising this powdery dispersant premixedwith powdery materials such as hydraulic compounds, aggregate etc. hasbeen developed.

[0005] However, there are cases where the monovalent metal salt of apolycarboxylic acid-based copolymer is hardly dry-powdered at roomtemperature, or even if it can be dry-powdered, the long-term shelfstability thereof prior to use, that is, the absence of adhesion(pressure resistance) attributable to the pressure in a package and theabsence of adhesion and deterioration in dispersibility (humidityresistance) attributable to moisture absorption, is not satisfied inhigh levels.

[0006] As the method of obtaining a powdery dispersant, JP-B 2669761(JP-A 6-239652) discloses a method of spray-drying a liquidpolycarboxylic acid-based copolymer and inorganic powder, JP-A 9-309756discloses a method of converting a copolymer consisting of apolyalkylene glycol alkenyl ether having a few alkylene oxide moleculesadded thereto and maleic anhydride into a polyvalent metal salt, JP-A11-310444 discloses a method of using a water-soluble vinyl copolymer incombination with a water-sparingly-soluble, specific metal salt ormetalhydroxide, and JP-A 2000-26145 discloses a method of dry-powdering a(meth)acrylate-based cement dispersant having a specific structurewherein the average number of alkylene oxide molecules added is 20 to109.

[0007] When a powdery dispersant is used in a large amount in largescale in a factory in an environment where the temperature and humidityare not necessarily regulated, there is demand for a powdery dispersantwith further improvements in pressure resistance and humidityresistance. On the other hand, there is also demand for a powderydispersant with dispersion performance which is particularly capable ofdispersing mortar in a hydraulic composition without conferringexcessive viscosity on the mortar, particularly for use in a largeamount of powder (particularly for use in grout mortar) which should beendowed with suitable viscosity and dispersed on the spot. In the priortechniques, however, a means of mixing an inorganic powder notcontributing to dispersion of hydraulic compounds or a means ofincorporating a large amount of salts is adopted, so there are worriesabout reduction in the efficiency of dispersion by the powderydispersant or the deterioration of physical properties which may becaused by the powdery dispersant after hardening of the dispersantsystem.

[0008] The powdery dispersant is required to have the long-term shelfstability thereof prior to use, that is, the absence of adhesion(pressure resistance) attributable to the pressure in a package and theabsence of adhesion and deterioration in dispersibility (humidityresistance) attributable to moisture absorption, but the conventionalpowdery dispersants, particularly comprising a monovalent metal salt ofpolycarboxylic acid-based copolymer, are still poor in pressureresistance and humidity resistance. Further, when dry powdering isconducted industrially, it is important that the viscosity of an aqueoussolution of starting materials is not increased to such an extent as notto hinder pumping etc., and further when the powdery dispersant is usedin grout mortar, the resulting hydraulic composition just after kneadingis required to have high flowability and suitable separation resistance,but the conventional dispersants are still not satisfactory for theserequirements.

SUMMARY OF THE INVENTION

[0009] The object of the present invention is to provide a powderydispersant which is excellent in pressure resistance and humidityresistance without hindering pumping etc., even if a polycarboxylic acidcopolymer hardly dry-powdered at room temperature is industriallydry-powdered, and which can confer stable dispersibility on a hydrauliccomposition, in particular on a hydraulic composition for mortar grout.

[0010] The present invention relates to a powdery dispersant forhydraulic compositions. The powdery dispersant encompasses dispersants(I) and (II).

[0011] The dispersant (I) is a powdery dispersant for a hydrauliccomposition, which comprises at least one copolymer obtainable bypolymerizing at least one vinyl monomer (a) represented by the formula(1):

[0012] wherein R¹ and R² represent a hydrogen atom or a methyl group, R³represents a hydrogen atom or —COO(AO)_(n)X, m is a number of 0 to 2, pis a number of 0 or 1, AO represents a C₂₋₄ oxyalkylene group or anoxystyrene group, n is the average mole number of added groups and is anumber of 2 to 300 and X represents a hydrogen atom or a C₁₋₁₈ alkylgroup;

[0013] with at least one vinyl monomer (b) represented by the formula(2):

[0014] wherein R⁴, R⁵ and R⁶ are the same as or different from oneanother and each represent a hydrogen atom, a methyl group or—(CH₂)_(m1)COOM² in which —(CH₂)_(m1)COOM² may be combined with —COOM¹or another —(CH₂)_(m1)COOM² to produce an anhydride, M¹ and M² of thesegroups not being present, M¹ and M² represent a hydrogen atom or apolyvalent metal and m₁ is a number of 0 to 2,

[0015] in which the average mole number of C₂₋₄ oxyalkylene groups oroxystyrene groups added to the dispersant molecule is 45 to 150, theratio of monomer (a) to monomer (b) ranges in (a)/[(a)+(b)]×100 of 15 to45 (mole-%) and at least part of the copolymers is a polyvalent metalsalt.

[0016] In the dispersant (I), the ratio of the monomer (a) to the sumtotal of (a)+(b) ranges preferably in (a)/[(a)+(b)]×100 of 20 to 35 mole%. Further, all the copolymers are preferably polyvalent metal salts.

[0017] The dispersant (II) is a powdery dispersant for a hydrauliccomposition, which comprises at least one copolymer obtainable bypolymerizing at least one vinyl monomer (a) represented by the formula(1):

[0018] wherein R¹ and R² represent a hydrogen atom or a methyl group, R³represents a hydrogen atom or —COO(AO)_(n)X, m is a number of 0 to 2, pis a number of 0 or 1, AO represents a C₂₋₄ oxyalkylene group or anoxystyrene group, n is the average mole number of added groups and is anumber of 2 to 300 and X represents a hydrogen atom or a C₁₋₁₈ alkylgroup;

[0019] with at least one vinyl monomer (b) represented by the formula(2):

[0020] wherein R⁴, R⁵ and R⁶ are the same as or different from oneanother and each represent a hydrogen atom, a methyl group or—(CH₂)_(m1)COOM² in which —(CH₂)_(m1)COOM² may be combined with —COOM¹or another —(CH₂)_(m1)COOM² to produce an anhydride, M¹ and M² of thesegroups not being present, M¹ and M² represent a hydrogen atom or amonovalent metal and m₁ is a number of 0 to 2,

[0021] in which the average mole number of C₂₋₄ oxyalkylene groups oroxystyrene groups added to the dispersant molecule is 50 to 150,(a)/[(a)+(b)]×100 ranges from 15 to 45 (mole %) and at least part of thecopolymer is a monovalent metal salt.

[0022] In the dispersant (II), (a)/[(a)+(b)]×100 ranges from 20 to 45mole %.

[0023] In the dispersant of the present invention, the average molenumber of C₂₋₄ oxyalkylene groups or oxystyrene groups added is 60 to130 or 60 to 115. Preferably, the powdery dispersant comprises acopolymer obtained from starting monomers containing 98 to 100% byweight of the monomers (a) and (b), or comprises 50 to 100% by weight ofdispersant particles whose diameter is 500 Mm or less.

[0024] The present invention also provides a hydraulic compositioncomprising the above-described powdery dispersant and a hydrauliccomposition, use of the above-described powdery dispersant as adispersant for a hydraulic composition and a method of dispersing ahydraulic composition by the above-described powdery dispersant.

[0025] The powdery dispersant of the present invention comprises atleast one copolymer obtained by polymerizing at least one vinyl monomer(a) represented by the formula (1) with at least one vinyl monomer (b)represented by the formula (2), wherein (a)/[(a)+(b)]×100 ranges from 15to 45 (mole-%), at least part of the copolymer is a monovalent salt or apolyvalent metal salt and the average mole number of C₂₋₄ oxyalkylenegroups or oxystyrene groups added is 45 to 150 when at least part of thecopolymer is a polyvalent metal salt or 50 to 150 when at least part ofthe copolymer is a monovalent metal salt.

[0026] The polyvalent metal salt is preferably divalent. When thecompolymer is a monovalent metal salt in part, the number of AO mayrange peferably from 80 to 150.

DETAILED DESCRIPTION OF THE INVENTION

[0027] First, with respect to the dispersant (I), the present inventorsfocused their attention on the fact that a polyvalent metal salt of apolycarboxylic acid-based dispersant is easily dry-powdered withoutlowering dispersibility, and they attempted to determine the mostsuitable structure of the polycarboxylic acid-based dispersant forbringing about pressure resistance and humidity resistance in goodbalance. As a result, the present inventors found that the added molenumber of C₂₋₄ oxyalkylene groups or oxystyrene groups (referred tohereinafter as specific AO groups) present in the dispersant and thecopolymer molar ratio M_(a) (mole-%) of the monomer (a) in thedispersant are significantly involved in giving rise to pressureresistance and humidity resistance. That is, pressure resistance tendsto improve as the number of specific AO groups added is increased andM_(a) is decreased, while humidity resistance tends to improve as thenumber of specific AO groups added is increased and M_(a) is increased.Then, the average number n_(M) of specific AO groups added in thedispersant was defined as 45 to 150, and M_(a) as 15 to 45 mole-%, andin these ranges, pressure resistance and humidity resistance wereachieved in good balance. In the dispersant satisfying this definition,the present inventors further defined use of a polyvalent metal salt ofsaid copolymer in order to achieve good dry powdering and gooddispersibility.

[0028] Further, with respect to the dispersant (II), the presentinventors determined that the average number nM of specific AO groupsadded in the dispersant is in the range of 50 to 150, and M_(a) is 15 to45 (mole-%), and in these ranges, pressure resistance and humidityresistance were achieved in good balance. In the dispersant satisfyingthis definition, the present inventors further defined use of amonovalent metal salt of said copolymer in order to achieve gooddispersibility. Hereinafter, the monomers (a) and (b), the copolymersetc. are described.

[0029] [Monomer (A)]

[0030] The monomer (A) represented by formula (1) includes (half)esterified products of a polyalkylene glycol terminated by an alkylgroup, such as methoxypolyethylene glycol, methoxypolypropylene glycol,methoxypolybutylene glycol, methoxypolystyrene glycol andethoxypolyethylene polypropylene glycol with (meth)acrylic acid ormaleic acid; etherified products thereof with 3-methyl-3-butenyl alcoholor (meth)allyl alcohol; or adducts having ethylene oxide or propyleneoxide added to (meth)acrylic acid, maleic acid, 3-methyl-3-butenylalcohol or (meth)allyl alcohol. R₃ is preferably a hydrogen atom, p ispreferably 1, and m is preferably 0. AO is preferably an oxyethylenegroup. The monomer (a) is preferably an esterified product of alkoxy,particularly methoxypolyethylene glycol with (meth)acrylic acid. Two ormore monomers (a) different in “n” may be used as a mixture thereof. nis preferably 5 to 200, more preferably 8 to 150.

[0031] <Monomer (b)>

[0032] The monomer (b) represented by formula (2) is preferably amonocarboxylic acid monomer such as (meth)acrylic acid, crotonic acidetc., a dicarboxylic acid monomer such as maleic acid, itaconic acid,fumaric acid etc., or an anhydride thereof or a polyvalent metal saltthereof, for example an alkaline earth metal salt, more preferably(meth)acrylic acid or a polyvalent salt thereof, maleic acid or apolyvalent metal salt thereof and maleic anhydride, more preferably(meth)acrylic acid or an alkaline earth metal salt thereof, and mostpreferably (meth)acrylic acid.

[0033] Further, the monomer (b) may also be a monovalent metal salt suchas alkali metal salt, more preferably (meth) acrylic acid, maleic acid,maleic anhydride and most preferably (meth) acryl acid or an alkalimetal salt thereof such as sodium salt, potassium salt etc.

[0034] <Copolymer>

[0035] The copolymers used in the powdery dispersant of the presentinvention can be produced in a known method by using the monomers (a)and (b). A plurality of monomers (a) and (b) can be used. Examples ofmethods for producing the same include solution polymerization methodsexemplified in Japanese Patent Application Laid-Open No. 59-162163,Japanese Patent Application Laid-Open No. 62-70250, Japanese PatentApplication Laid-Open No. 62-78137 and U.S. Pat. Nos. 4,870,120 and5,137,945. That is, the copolymers can be produced by polymerizing thevinyl monomers (a) and (b) in the ratio defined above in a suitablesolvent. For example, the monomers may be reacted at 50 to 100° C. for0.5 to 10 hours in a nitrogen atmosphere in water or C₁₋₄ lower alcoholin the presence of a polymerization initiator such asammoniumpersulfate, hydrogen peroxide etc. and if necessary in thepresence of sodium hydrogen sulfite, mercaptoethanol etc.

[0036] For production of the copolymers of the present invention,copolymerizable monomers such as acrylonitrile, (meth)acrylamide,styrene, alkyl (meth)acrylates (C₁₋₁₂ acrylates which may have ahydroxyl group), methallyl sulfonic acid, styrene sulfonic acid,phosphoethyl methacrylate and sulfoethyl methacrylate can be used incombination with the monomers (a) and (b), but the starting monomerscomprise preferably 98 to 100% by weight of the monomers (a) and (b).

[0037] The weight average molecular weight of the copolymers used in thepowdery dispersant of the present invention [determined usingpolyethylene glycol standards in gel permeation chromatography withcolumns G4000 PWXL+G2500 PWXL (Tosoh Corp.) and eluent 0.2 M phosphatebuffer/acetonitrile=7/3 (ratio by volume)] is preferably in the range of6,000 to 1,000,000, more preferably 10,000 to 200,000 and mostpreferably 55,000 to 150,000 from the viewpoint of dispersibility andsurface hardness.

[0038] At least part of the copolymer of the present invention forms amonovalent or polyvalent metal salt. The salts may be derived frommonomers or formed through neutralization after copolymerizationreaction.

[0039] The polyvalent metal includes calcium, magnesium, aluminum etc.,and calcium is particularly preferable. In consideration ofdry-powdering, the degree of polymerization with polyvalent metals ispreferably 5% or more, more preferably 10% or more, more preferably 20%or more, more preferably 40% or more and most preferably 50% or more. Ifthe degree of polymerization is too high, the resulting copolymers arepoor in pumping because of excessive thickening, so the degree ofpolymerization is preferably 100% or less, more preferably 90% or less.This degree of neutralization is the ratio of the number of moles oftotal charged polyvalent metal salts to the number of moles of totalcarboxyl groups in the powdery dispersant, and can be calculated byquantifying the polyvalent metal salts in the powdery dispersant byinduction binding plasma emission analysis.

[0040] The monovalent metal is preferably an alkali metal, morepreferably sodium. The degree of neutralization is preferably 40 to100%, more preferably 50 to 90% and most preferably 50 to 80%.

[0041] In the powdery dispersant of the present invention, a pluralityof copolymers different in n_(M) and M_(a) can be used. If necessary,acid-form copolymers which are not polyvalent metal salts can also beused in combination.

[0042] <Powdery Dispersant>

[0043] The resulting copolymers can be used as the dispersant afterbeing powdered in a usual manner. Specifically, a spray drying method, afilm drying method etc. can be mentioned. At the time of production, thecopolymers can be powdered if necessary together with organic and/orinorganic compounds as carriers, but these carriers are preferably notused. The organic compounds are preferably high-molecular compounds, andthe inorganic compounds are preferably blast furnace slag, siliceoussand, silica powder, fly ash and calcium carbonate. When carriers areused, the amount thereof in the finally obtained powdery dispersant ispreferably 1 to 80% by weight, particularly 5 to 30% by weight.

[0044] When the monomer (a) where n is 110 or more is used in thedispersant (II), it is preferable that a sticky film of thepolycarboxylic acid copolymers is formed on a support, and the film ispowdered by reducing the viscosity of the film. At the time ofproduction, the copolymers can be powdered if necessary together withorganic and/or inorganic compounds as carriers, but these carriers arepreferably not used. The organic compounds are preferably high-molecularcompounds, and the inorganic compounds are preferably blast furnaceslag, siliceous sand, silica powder, fly ash and calcium carbonate. Whencarriers are used, the amount thereof in the finally obtained powderydispersant is preferably 1 to 80% by weight, particularly 5 to 30% byweight.

[0045] In the powdery dispersant (I) of the present invention, theaverage number n_(M) of specific AO molecules added is 45 to 150, andfor pressure resistance and humidity resistance, the n_(M) is 50 ormore, preferably 60 or more and most preferably 70 or more. Forsuppressing thickening of mortar and for pumping during production ofthe copolymers, the n_(M) is 150 or less, preferably 130 or less, morepreferably 115 or less and most preferably 100 or less.

[0046] In the powdery dispersant (II) of the present invention, theaverage number n_(M) of specific AO molecules added is 50 to 150, andfor pressure resistance and humidity resistance, the n_(M) is 60 ormore, preferably 70 or more, more preferably 75 or more and mostpreferably 80 or more. For pressure resistance and pumping duringproduction of the copolymers, the nM is 130 or less, preferably 115 orless and more preferably 100 or less.

[0047] The average number n_(M) of specific AO molecules added may beadjusted by being mixed with another AO including compound.

[0048] In the powdery dispersant (I) of the present invention, it ispreferable for humidity resistance that the ratio M_(a), that is, thetotal monomer (a) to the sum total of the monomers (a)+(b) is selectedsuch that (a)/[(a)+(b)]×100 may be in the range of 15 to 45 mole-%. Forpressure resistance, the M_(a) is preferably 40 mole-% or less. In thepowdery dispersant (I), the ratio of the total monomer (a) to the sumtotal of the monomers (a)+(b), (a)/[(a)+(b)]×100, may be in the range of20 to 35 mole-%.

[0049] In the powdery dispersant (II), the ratio M_(a) of the totalmonomer (a) to the sum total of the monomers (a)+(b) may be selectedsuch that (a)/[(a)+(b)]×100 is in the range of 15 to 45 mole-%,preferably 20 mole-% or more for powder drying and humidity resistance.For pressure resistance, the M_(a) is preferably 45 mole-% or less.

[0050] The n_(M) and M_(a) can also be calculated from the ratio ofcharged monomers (a) to (b) or determined by analyzing the finaldispersant in ¹H-NMR. In the present invention, the n_(M) and M_(a) ofthe dispersant were determined by analysis in ¹H-NMR.

[0051] In molecular design where two or more monomers different in “n”are used as the monomer (a), the n_(M) can be approximately estimatedfrom the ratio of ^(Ε)[mole-% of the monomer (a) of number j of added AOmolecules ×number j of added AO molecules to [mole-% of the monomer (a)of number j of added AO molecules].

[0052] In the present invention, monovalent metal salts (preferablysodium salts) of the copolymers obtainable by polymerizing at least onevinyl monomer (a) with at least one vinyl monomer (b) can be used incombination. Some copolymers (acid form) consisting of the monomers (a)and (b) or some monovalent metal salts thereof are hardly dry-powderedat room temperature, but dry-powdering can be improved by simultaneouslyusing copolymers which are polyvalent metal salts at least partially,preferably entirely. The average value n_(MP) of n of the total monomers(a) constituting the polyvalent metal salts is preferably greater thanthe average value n_(MM) of n of the total monomers (a) in thecopolymers (acid form) and/or monovalent metal salts thereof (that is,n_(MP)>n_(MM)) more preferably greater by 1 or more, further preferablyby 2 or more and most preferably by 5 or more.

[0053] To allow the polyvalent metal salt-type copolymers to be presentin the powdery dispersant of the present invention, the monovalent metalsalt-type copolymers may previously be mixed with the polyvalent metalsalt-type copolymers and then dry-powdered, or the monovalent metalsalt-type copolymers having low degrees of neutralization may beconverted into copolymers containing polyvalent metal salts byneutralization with a polyvalent metal hydroxide, and insofar as thepolyvalent metal salt-type copolymers are finally contained in thepowdery dispersant, any method can be used.

[0054] From the viewpoint of anti-foaming properties, an anti-foamingagent is desirably added to the powdery dispersant of the presentinvention. The anti-foaming agent includes those based on lower alcoholssuch as methanol and ethanol, silicones such as dimethyl silicone oiland fluorosilicone oil, mineral oils such as materials compounded withmineral oils and surfactants, phosphates such as tributyl phosphate,fatty acids or esters thereof, such as oleic acid, sorbitan oleic acidmonoester, sorbitan oleic acid monoester, polyethylene glycol fattyester and polyethylene/polypropylene glycol fatty ester, and nonionicmaterials such as polypropylene glycol, and polyethylene/polypropyleneglycol alkyl ether. The anti-foaming agent is preferably fatty acids oresters thereof, more preferably polyethylene/polypropylene glycol fattyesters. The amount of the anti-foaming agent added to the powderydispersant is preferably 0.01 to 10% by weight, more preferably 0.05 to5% by weight and most preferably 0.1 to 3% by weight.

[0055] From the viewpoint of water solubility for practical use, thepowdery dispersant of the present invention comprises preferably 50 to100% by weight, more preferably 70 to 100% by weight and most preferably90 to 100% by weight of the powdery dispersant whose particle diameteris 500 μm or less.

[0056] The powdery dispersant of the present invention can be used afterbeing premixed with hydraulic compounds such as cement, gypsum etc. andif necessary with aggregate. The premix can be used in self-levelingmaterials, grout for tunnels, spraying mortar, shrink-free materials,refractory, gypsum plaster etc. The hydraulic compounds include Portlandcement, blast furnace cement, silica cement, fly ash cement, aluminacement, natural gypsum, gypsum byproducts, etc., preferably Portlandcement, alumina cement and natural gypsum, more preferably Portlandcement and alumina cement.

[0057] The powdery dispersant of the present invention is used in anamount of preferably 0.01 to 5% by weight, more preferably 0.02 to 3% byweight in terms of solid content in hydraulic compounds such as cement,gypsum etc.

EXAMPLES Production Example 1

[0058] A glass reaction vessel equipped with a thermometer, a stirrer, adropping funnel, a nitrogen inlet pipe and a reflux condenser wascharged with 475 parts by weight of water, and the atmosphere thereinwas replaced by nitrogen. Then, the vessel was heated to 58° C. in anitrogen atmosphere, and 3 solutions, that is, a mixture of 295 parts byweight of methoxy polyethylene glycol monomethacrylate (monomer (a),n=10) and 76.7 parts by weight of methacrylic acid, 44.9 parts by weightof 5% aqueous 2-mercaptoethanol, and 85.2 parts by weight of 5% aqueousammonium persulfate, were simultaneously added dropwise thereto over 90minutes. Then, the mixture was aged at the same temperature for 1 hour,and then 13.1 parts by weight of 5% aqueous ammonium persulfate wasadded dropwise thereto over 30 minutes and thereafter aged at the sametemperature for 2 hours. The reaction solution was neutralized by adding52.7 parts by weight of calcium hydroxide and then cooled to give acopolymer having a weight average molecular weight of 36000 [Ca salt(degree of neutralization of 80%)] (copolymer 2 in Table 1). The othersimilar copolymer Ca salts having degrees of neutralization of 80+10%,shown in Table 1, were produced in an analogous manner.

Production Example 2

[0059] The same glass reaction vessel as in Production Example 1 wascharged with 266 parts by weight of water, and the atmosphere thereinwas replaced by nitrogen. Then, the vessel was heated to 80° C. in anitrogen atmosphere, and 3 solutions, that is, a mixture of 508.5 partsby weight of 60% methoxy polyethylene glycol monomethacrylate (monomer(a), n=120), 42.2 parts by weight of methoxy polyethylene glycolmonomethacrylate (monomer (a), n=9) and 36.6 parts by weight ofmethacrylic acid, 44.3 parts by weight of 5% aqueous 2-mercaptoethanol,and 51.7 parts by weight of 5% aqueous ammonium persulfate, weresimultaneously added dropwise thereto over 90 minutes. Then, the mixturewas aged at the same temperature for 1 hour, and then 25.8 parts byweight of 5% aqueous ammonium persulfate was added dropwise thereto over30 minutes and thereafter aged at the same temperature for 2 hours. Thereaction solution was neutralized by adding 25.2 parts by weight ofcalcium hydroxide and then cooled to give a copolymer having a weightaverage molecular weight of 68000 [Ca salt (degree of neutralization of80%)] (copolymer 17 in Table 1) The other similar copolymer Ca saltshaving degrees of neutralization of 80±10%, shown in Table 1, wereproduced in an analogous manner.

Production Example 3

[0060] Copolymer 8 [Ca salt (degree of neutralization of 80%)] in Table1 was produced in the same manner as in the method of producing awater-soluble vinyl copolymer described in Japanese Patent ApplicationLaid-Open No. 7-309656 except that calcium hydroxide was used in placeof sodium hydroxide.

Production Example 4

[0061] Copolymer 22 [Ca salt (degree of neutralization of 80%)] in Table1 was produced in the same manner as in the production method describedin column 0042 in Japanese Patent Application Laid-Open No. 9-309756.

[0062] Table 1 TABLE 1 Monomer (a) (a)-1 (a)-2 Monomer (b) Others ChargeCharge Charge Charge Copolymer molar molar molar molar Weight %Production No. Type ratio n Type ratio n Type ratio Type ratio (a) + (b)Salt Mw Example 1 MEPEG 38 10 — — — MAA 62 — — 100 Na Salt 36000 1 2MEPEG 38 10 — — — MAA 62 — — 100 Ca Salt 36000 3 MEPEG 33 25 — — — MAA67 — — 100 Na Salt 46000 4 MEPEG 33 25 — — — MAA 67 — — 100 Ca Salt46000 5 MEPEG 30 60 — — — MAA 70 — — 100 Na Salt 21000 6 MEPEG 30 60 — —— MAA 70 — — 100 Ca Salt 21000 7 MEPEG 20 50 — — — MAA 75 MSA 5 98.8 CaSalt 61000 3 8 MEPEG 20 50 — — — MAA 65 MSA 15 96.4 Ca Salt 53000 9MEPEG 30 90 — — — MAA 70 — — 100 Na Salt 41000 1 10 MEPEG 30 90 — — —MAA 70 — — 100 Ca Salt 41000 11 MEPEG 30 100 — — — MAA 70 — — 100 CaSalt 63000 12 MEPEG 20 120 — — — MAA 80 — — 100 Na Salt 66000 13 MEPEG20 120 — — — MAA 80 — — 100 Ca Salt 66000 14 MEPEG 35 120 — — — MAA 65 —— 100 Ca Salt 72000 15 MEPEG 15 140 — — — MAA 85 — — 100 Ca Salt 5900016 MEPEG 15 160 — — — MAA 85 — — 100 Ca Salt 89000 17 MEPEG 10 120 MEPEG15 9 MAA 75 — — 100 Ca Salt 68000 2 18 MEPEG 15 90 MEPEG 15 25 MAA 70 —— 100 Ca Salt 64000 19 MEPEG 10 90 MEPEG 15 60 MAA 75 — — 100 Ca Salt61000 20 MEPEG 55 120 — — — MAA 45 — — 100 Ca Salt 82000 1 21 MEPEG 4560 — — — MAA 55 — — 100 Ca Salt 45000 22 METPEG 30 70 — — — MA 70 — —100 Ca Salt 59000 4

[0063] (Note) The meanings of the symbols in the table are as follows.The degree of neutralization of any copolymer salts in the table is80±10%.

[0064] MEPEG: methoxy polyethylene glycol monomethacrylate

[0065] METPEG: methoxy polyethylene glycol monoallyl ether

[0066] MAA: methacrylic acid

[0067] MSA: methallyl sulfonic acid

[0068] MA: maleic anhydride

[0069] Mw: weight average molecular weight

[0070] Production Example 5

[0071] A glass reaction vessel equipped with a thermometer, a stirrer, adropping funnel, a nitrogen inlet pipe and a reflux condenser wascharged with 202.2 parts by weight of water, and the atmosphere thereinwas replaced by nitrogen. Then, the vessel was heated to 80° C. in anitrogen atmosphere, and 3 solutions, that is, a mixture of 570.7 partsby weight of 60% methoxy polyethylene glycol monomethacrylate (monomer(a), n 75) and 34.7 parts by weight of methacrylic acid, 62.9 parts byweight of 5% aqueous 2-mercaptoethanol, and 68.8 parts by weight of 5%aqueous ammonium persulfate, were added simultaneously added dropwisethereto over 90 minutes. Then, the mixture was aged at the sametemperature for 1 hour, and then 23 parts by weight of 5% aqueousammonium persulfate was added dropwise thereto for 30 minutes andthereafter aged at the same temperature for 2 hours. The reactionsolution was neutralized by adding 23.5 parts by weight of 48% aqueoussodium hydroxide, and then 7.8 parts by weight of 35% aqueous hydrogenperoxide was added thereto and the mixture was heated to 90° C., kept atthe same temperature for 1 hour, and cooled to give a copolymer having aweight average molecular weight of 33000 [Na salt (degree ofneutralization of 70%)] (Invented Product 4 in Table 4). The othersimilar copolymers having degrees of neutralization of 70+-10%, shown inTable 4, were produced in an analogous manner.

Production Example 6

[0072] The same glass reaction vessel as in Production Example 5 wascharged with 248.5 parts by weight of water, and the atmosphere thereinwas replaced by nitrogen. Then, the vessel was heated to 80° C. in anitrogen atmosphere, and 3 solutions, that is, a mixture of 502.2 partsby weight of 60% methoxy polyethylene glycol monomethacrylate (monomer(a), n=120), 41.5 parts by weight of methoxy polyethylene glycolmonomethacrylate (monomer (a), n=9) and 36 parts by weight ofmethacrylic acid, 39.2 parts by weight of 5% aqueous 2-mercaptoethanol,and 76.2 parts by weight of 5% aqueous ammonium persulfate, weresimultaneously added dropwise thereto over 90 minutes. Then, the mixturewas aged at the same temperature for 1 hour, and then 20.3 parts byweight of 5% aqueous ammonium persulfate were added dropwise theretoover 30 minutes and thereafter aged at the same temperature for 2 hours.The reaction solution was neutralized by adding 24.4 parts by weight of48% aqueous sodium hydroxide, and then 5 parts by weight of 35% aqueoushydrogen peroxide was added thereto. The mixture was heated to 90° C.,kept at the same temperature for 1 hour, and cooled to give a copolymerhaving a weight average molecular weight of 68000 [Na salt (degree ofneutralization of 70%)] (Invented Product 15 in Table 4). The othersimilar copolymers having degrees of neutralization of 70±10%, shown inTable 4, were produced in an analogous manner.

[0073] Production Example 7

[0074] A copolymer [Na salt (degree of neutralization of 70%)] asComparative Product 5 in Table 4 was produced in the same manner as inthe method of producing a water-soluble vinyl copolymer described inJapanese Patent Application Laid-Open No. 7-309656.

Production Example 8

[0075] A copolymer [Na salt (degree of neutralization of 70%)] asInvented Product 18 in Table 4 was produced in the same manner as in theproduction method described in column 0042 in Japanese PatentApplication Laid-Open No. 9-309756 except that sodium hydroxide wasadded in place of calcium hydroxide.

Example 1

[0076] The copolymers shown in Table 1 were combined as shown in Table 2to prepare dispersants which were then evaluated in the followingmanner. The results are shown in Table 2. Further, the n_(M) and M_(a)of each dispersant were measured in the following methods.

[0077] (A) n_(M) of the Dispersant.

[0078] The dispersant dissolved in water was dried under reducedpressure in a nitrogen atmosphere, dissolved at a concentration of 3 to4% in heavy water and measured by ¹H-NMR. From the integrated area of analkoxy group (in this case, methoxy group) peak and the integrated areaof an alkylene oxide group (in this case, ethylene oxide group) peak,the total number of H atoms in the ethylene oxide group was determinedand then divided by the number of hydrogen atoms contained in oneethylene oxide group to give n_(M) of the dispersant. Measurement by¹H-NMR was conducted using “UNITY-INOVA500” (500 MNHZ) manufactured byVarian Co., Ltd. under the following conditions: the number of datapoints, 64000; the measurement range, 10000.0 Hz; the pulse width (450pulse), 60 Psec.; the pulse delay time, 30 sec.; and the measurementtemperature, 25.0° C.

[0079] (B) M_(a) of the Dispersant

[0080] The dispersant dissolved in water was dried at room temperaturein a nitrogen atmosphere, dissolved in heavy water and measured by¹H-NMR (under the same conditions as described above). From anaccumulated area (s) of an alkoxy group (in this case, methoxy group)peak and an accumulated area (S) of a main-chain alkyl group (in thiscase, methyl group) peak, [(S−s)/S]×100 was calculated to determine theratio M_(a) of the monomer (a) to the monomer (b) in the entiredispersant.

[0081] (1-1) Dry-powdering Properties

[0082] An aqueous solution of each dispersant in Table 1, whoseconcentration and amount were previously regulated so as to form a filmof about 1 mm in thickness after drying, was placed in a flat vessel anddried at 105° C. for 2 hours. From the dried dispersant film, a testspecimen of 40 mm×15 mm was prepared and put between fingers at a siteapart by about 1 cm from one end in the longer direction, and the testspecimen was bent by bending force exerted from the other end. This testwas conducted at a predetermined film temperature, and the behavior wasobserved and evaluated in the following criteria. “Capable of powdering”was given to a specimen broken by the bending force, and “Not capable ofpowdering” was given to a specimen simply bent without breakage. Thetemperature of the film was regulated by leaving it in a non-hygroscopicstate in a thermostatic chamber at a predetermined temperature for 2hours.

[0083] A: Capable of powdering at 40° C.

[0084] B: Capable of powdering at 30° C., but liquefying or not capableof powdering at 40° C.

[0085] C: Capable of powdering at 20° C., but liquefying or not capableof powdering at 30° C.

[0086] D: Capable of powdering at 10° C., but liquefying or not capableof powdering at 20° C.

[0087] E: Not capable of powdering at 10° C.

[0088] F: Liquefying at 10° C.

[0089] (1-2) Pressure Resistance

[0090] 250 cm³ dispersant was charged into a polyethylene bag (volume:250 cm³) and, in a sealed state, left at 20° C. with a loading of 1000kgf/m². After 1 day and after 7 days, the degree of sifting through a1410 μm sieve was measured and evaluated for pressure resistance underthe following criteria.

[0091] A: Degree of sifting of 95% (exclusive) to 100% (inclusive)

[0092] B: Degree of sifting of 90% to 95%

[0093] C: Degree of sifting of 80% to 90%

[0094] D: Degree of sifting of 70% to 80%

[0095] E: Degree of sifting of 50% to 70%

[0096] F: Degree of sifting of 50% or less

[0097] (1-3) Humidity Resistance

[0098] 50 g powdery dispersant (previously dried at 105° C. for 2 hours)was placed in a 300 ml beaker and left for 7 days in an open system in athermostatic chamber at 25° C. under 40% humidity, and the amount ofabsorbed water therein was determined from a change in the weightthereof, to evaluate humidity resistance under the following criteria.

[0099] A: Water content of 2% or less (solid content: 98% or more)

[0100] B: Water content of 2% (exclusive) to 4% (inclusive) (solidcontent: 96% (inclusive) to 98% (exclusive))

[0101] C: Water content of 4% to 6% (solid content: 94% to 96%)

[0102] D: Water content of 6% to 8% (solid content: 92% to 94%)

[0103] E: Water content of 8% to 10% (solid content: 90% to 92%)

[0104] F: Water content of more than 10% (solid content: less than 90%)

[0105] (1-4) Pumping (pump transportability)

[0106] The viscosity of an aqueous solution of the dispersant (activeingredient: 40% by weight) at 20° C. was measured with a Brookfieldrotational viscometer, to evaluate pump transportability under thefollowing criteria.

[0107] A: Viscosity of 400 mPa·s (inclusive) to 420 mPa·s (exclusive)

[0108] B: Viscosity of 420 mPa·s to 450 mPa·s

[0109] C: Viscosity of 450 mPa·s to 500 mPa·s

[0110] D: Viscosity of 500 mPa·s to 600 mPa·s

[0111] E: Viscosity of 600 mPa·s to 700 mPa·s

[0112] F: Viscosity of 700 mPa·s or more

[0113] (1-5) Separation Resistance

[0114] The dispersant, 360 g water, 800 g cement and 1800 g fineaggregate were kneaded in a mortar mixer (in accordance with JIS R5201.8), and the resulting mortar was packed in an inverted conicalcylinder (device for measuring the dropping time of the mortar) of 300mm in length having an upper inlet opening of 100 mm in diameter and alower discharge opening of 20 mm in diameter in such a state that thelower discharge opening was closed, and then the mortar was cut byrubbing on the face of the upper inlet opening. By opening the lowerdischarge opening, the mortar was gravitationally dropped to determinethe time (dropping time) elapsed until a hole in at least a part of themortar was recognized by observing the upper inlet opening. A longerdropping time is indicative of higher viscosity of the concrete, thusindicating higher resistance to material separation. The amount of thedispersant added was regulated such that the mortar flow value was 290mm±10 mm.

[0115] Table 2 TABLE 2 Dispersant Pressure Separa- Co- Co- Co- Dryresistance Humidity Pump tion re- polymer Weight polymer Weight polymerWeight M_(a) powder- After 1 After 7 resis- transport- sistance No. %No. % No. % (mol %) n_(M) ing days days tance ability (sec) ComparativeProducts 1-1 1 100 — — — — 37.0 9.2 F — — — — — 1-2 2 100 — — — — 37.610.2 E E F E A 5.1 1-3 3 100 — — — — 34.5 24.0 F — — — — — 1-4 1 75 1225 — — 32.1 37.0 F — — — — — 1-5 16 100 — — — — 15.6 159.7 A A A A F15.9 1-6 20 100 — — — — 56.0 120.9 A A A B F 17.0 Invented Products 1-18 100 — — — — 20.4 50.9 E E E E C 5.9 1-2 7 100 — — — — 21.0 50.9 E D EE C 5.7 1-3 1 65 12 25 13 10 30.9 47.8 E D E D A 6.0 1-4 1 20 21 80 — —42.2 48.9 D D E D C 6.1 1-5 17 100 — — — — 24.3 52.9 D D D D C 6.2 1-618 100 — — — — 24.6 59.1 D D D D D 6.1 1-7 1 60 12 20 13 20 31.2 55.3 DD E D A 6.3 1-8 6 100 — — — — 31.0 58.7 C C D C C 6.5 1-9 1 50 13 50 — —30.1 64.3 B C C C B 6.6 1-10 2 50 12 50 — — 29.4 64.6 B B C B A 6.7 1-112 50 13 50 — — 29.5 65.9 B B C B C 6.7 1-12 2 25 10 75 — — 32.6 71.0 A BB B D 8.0 1-13 19 100 — — — — 24.1 71.5 A B B A D 8.3 1-14 4 25 10 75 —— 29.2 72.6 A B B A D 8.7 1-15 5 25 10 75 — — 31.0 81.4 A A B A D 8.31-16 6 25 10 75 — — 31.4 81.9 A A A A D 8.2 1-17 9 25 10 75 — — 30.889.1 A A A A D 9.5 1-18 10 100 — — — — 29.1 90.7 A A A A D 9.7 1-19 1115 13 85 — — 20.8 115.9 A A A A D 8.6 1-20 13 100 — — — — 21.1 121.3 A AA A D 10.3 1-21 14 100 — — — — 34.1 119.4 A A A A D 15.5 1-22 15 100 — —— — 14.3 141.3 A A A A E 14.2 1-23 22 100 — — — — 31.0 71.0 A A A A D15.9

[0116] As shown in Table 2, the dispersants as Comparative Products 1-1,1-3 and 1-4 where the n_(M) is small cannot be dry-powdered, andComparative Product 2 even containing a polyvalent metal salt is poor inpressure resistance when the n_(M) is low. Further, Comparative Product1-5 where the n_(M) is large is poor in pumping (pump transportability).On the other hand, Invented Products 1-1 to 1-23 are excellent in drypowdering, pressure resistance, humidity resistance, pumptransportability and separation resistance.

Example 2

[0117] 100 parts by weight of rapid-hardening Portland cement (TaiheiyoCement Corp.), 100 parts by weight of fine aggregate [siliceous sand (amixture of Nos. 3, 4 and 5, manufactured by Takeori Kogyo-sho)], 0.0025part by weight of a thickener [Metrose (Shin-Etsu Chemical Co., Ltd.)],0.02 part by weight of a retarder [sodium citrate (special grade)], 5parts by weight of an expansive material [Denka CSA (Denki KagakuKogyo)], 0.0015 part by weight of a foaming agent (metal aluminumpowder), the powdery dispersant in Table 3 and an anti-foaming agent[Foamlex 797 (Nicca Chemical Co., Ltd.)] in an amount shown in Table 3were mixed to produce a grout material. Water was added to the groutmaterial, and the mixture was kneaded for 3 minutes with a hand mixer togive slurry. This slurry was used in the following evaluation. Theresults are shown in Table 3.

[0118] (2-1) Flowability

[0119] The dropping time (sec.) was measured by “PC Grout Test Method(JCSE-F531)” according to Japanese Society of Civil Engineering.However, the amount of the powdery dispersant added was regulated suchthat the flow value measured according to “JIS R 5201 Cement PhysicalTest Method” was 250 mm +10 mm.

[0120] (2-2) Bleeding Ratio

[0121] Determined by “PC Grout Test Method (Polyethylene Bag Method)(JCSE-F532)” according to Japanese Society of Civil Engineering.

[0122] (2-3) Expansivity

[0123] Determined by “PC Grout Test Method (Vessel Method) (JCSE-F533)”according to Japanese Society of Civil Engineering.

[0124] (2-4) Compression Strength

[0125] The material aged for 28 days was measured according to “JIS R5201 Cement Physical Test Method”.

[0126] Table 3 TABLE 3 Powdery dispersant Dropping time (sec) Co- Co-Anti- M_(a) Just After After After Bleeding Expan- Compression polymerWeight polymer Weight foaming (mole after 30 60 90 ratio sivity strengthNo. No. % No. % agent %) n_(M) kneading minutes minutes minutes (%) (%)(N/mm²) 2-1 10 100 — — 0.3 29.1 90.7 6.0 8.3 11.0 14.1 less than 0.5+0.84 56 2-2 10 100 — — — 29.1 90.7 5.8 8.3 11.0 13.9 less than 0.5+0.83 52 2-3 1 50 13 50 0.3 30.1 65.9 5.8 8.1 10.6 13.4 less than 0.5+0.83 55 2-4 19 100 — — 0.3 24.1 71.5 5.6 7.9 10.4 13.2 less than 0.5+0.84 57 2-5 22 100 — — 0.3 31.0 71.0 5.1 7.2 9.8 11.5 less than 0.5+0.85 53 2-6 16 100 — — 0.3 15.6 160.0 7.1 10.7 16.5 18.6 less than 0.5+0.83 57

[0127] The weight-% of the anti-foaming agent is weight-% relative tothe total amount of the copolymer.

[0128] As shown in Table 3, when the powdery dispersant of the presentinvention is used in mortar grout, mortar grout excellent inflowability, bleeding ratio, expansivity and compression strength isobtained. In particular, when an anti-foaming agent is used, compressionstrength is stabilized. For use in mortar grout, Ca salts (Nos. 2-1 to2-4) of copolymers derived from ester type monomers indicate a longerdropping time and more stable separation resistance than those of a Casalt (No. 2-5) of a copolymer derived from ether type monomers. On theother hand, there is the case where the flowability of No. 2-6(Comparative Product) is deteriorated due to excessive thickening.

[0129] The invented products are excellent in pressure resistance,humidity resistance and pump transportability.

Example 3

[0130] Each copolymer shown in Table 4 was used as a dispersant andevaluated in the following manner. The results are shown in Table 5. Then_(M) and M_(a) of the dispersant were measured in the following method.

[0131] Table 4 TABLE 4 Copolymer monomer (a) Others (a)-1 (a)-2 monomer(b) Other-1 Other-2 Dispersant Charge Charge Charge Charge Charge M_(a)Pro- molar molar molar molar molar (mole duction Type ratio n Type ration Type ratio Type ratio Type ratio Mw %) n_(M) Example Compara- tiveproducts 1 MEPEG 20 10 — — — MAA 80 — — — — 39000 20.5 10.4 5 2 MEPEG 3535 — — — MAA 65 — — — — 42000 34.8 36.0 3 MEPEG 45 45 — — — MAA 55 — — —— 40000 45.2 45.8 4 MEPEG 5 75 — — — MAA 65 MSA 15 MAc 15 20000  5.174.1 5 MEPEG 5 75 MEPEG 10 30 MAA 65 MSA 15 MAc 5 19000 15.3 46.2 7 6MEPEG 10 75 MEPEG 15 8 MAA 60 MSA 10 MAc 5 22000 25.3 35.5 7 MEPEG 5 120MEPEG 20 10 MAA 75 — — — — 35000 24.6 33.1 6 8 MEPEG 60 100 — — — MAA 40— — — — 64000 61.0 101.1 5 Invented Products 1 MEPEG 13 56 — — — MAA 82MSA 5 — — 33000 13.2 55.4 7 2 MEPEG 13 56 — — — MAA 87 — — — — 3200012.8 55.8 3 MEPEG 25 65 — — — MAA 75 — — — — 40000 24.5 64.7 4 MEPEG 2075 — — — MAA 80 — — — — 33000 19.2 75.6 5 MEPEG 20 85 — — — MAA 80 — — —— 56000 20.0 84.6 6 MEPEG 20 100 — — — MAA 80 — — — — 62000 20.8 99.1 7MEPEG 20 115 — — — MAA 80 — — — — 65000 20.2 114.6 8 MEPEG 20 120 — — —MAA 80 — — — — 66000 20.7 121.0 5 9 MEPEG 35 120 — — — MAA 65 — — — —72000 34.8 119.1 10 MEPEG 15 130 — — — MAA 85 — — — — 63000 15.2 131.211 MEPEG 15 150 — — — MAA 85 — — — — 81000 15.3 148.9 12 MEPEG 30 90 — —— MAA 70 — — — — 41000 31.0 91.1 13 MEPEG 40 80 — — — MAA 60 — — — —38000 40.3 80.5 14 MEPEG 45 70 — — — MAA 55 — — — — 42000 44.0 69.8 15MEPEG 10 120 MEPEG 15 9 MAA 75 — — — — 68000 24.6 52.9 16 MEPEG 15 90MEPEG 15 25 MAA 60 — — — — 64000 29.4 56.8 6 17 MEPEG 10 90 MEPEG 15 60MAA 75 — — — — 61000 24.1 71.8 18 METPEG 35 70 — — — MA 65 — — — — 5500034.0 70.6 8

[0132] (Note) The meanings of the symbols in the table are shown below.Any copolymers in the table are sodium salts having degrees ofneutralization of 70±10%. In Comparative Product 4, the ratio of themonomer (a) +monomer (b) to the total monomers was 87.2% by weight; inComparative Product 5, the ratio of the monomer (a) +monomer (b) to thetotal monomers was 93.7% by weight; and in Comparative Product 6, theratio of the monomer (a) +monomer (b) to the total monomers was 96.2% byweight.

[0133] MEPEG: methoxy polyethylene glycol monomethacrylate

[0134] METPEG: methoxy polyethylene glycol monoallyl ether

[0135] MAA: methacrylic acid

[0136] MSA: methallyl sulfonic acid

[0137] MAc: methyl acrylate

[0138] MA: maleic anhydride

[0139] Mw: weight average molecular weight

[0140] Table 5 TABLE 5 Pressure resistance Humidity Pump Dry powderingAfter 1 day After 7 days resistance transportability Comparativeproducts 1 F — — — — 2 F — — — — 3 F — — — — 4 E E E F A 5 E E F F A 6 EF F F A 7 E F F F A 8 C C D A F Invented Products 1 E E E E A 2 D E F EA 3 C C E D A 4 C C D D A 5 C A C C A 6 C A C C A 7 C A D C B 8 A A D AC 9 A A D A C 10 A A A B C 11 A A A A D 12 C A C B A 13 C A C A B 14 C AC A B 15 C C E D A 16 C C D C A 17 C A C C A 18 C A A C A

[0141] As shown in Tables 4 and 5, Comparative Products 1 to 3 of lowdispersant n_(M) are poor in dry powdering; Comparative Product 4 ofhigh n_(M) but low M_(a) has an improvement in dry powdering but is poorin humidity resistance; Comparative Products 5 to 7 of low n_(M) onaverage, though using monomers of high n, are poor in pressureresistance and humidity resistance; and Comparative Product 8 of highM_(a) is poor in pump transportability. On the other hand, InventedProducts 1 to 18 are excellent in any items of dry powdering, pressureresistance, humidity resistance and pump transportability.

Example 4

[0142] The dispersants were prepared in the combinations shown in Table6 and evaluated in the same manner as in Example 3. The results areshown in Table 6.

[0143] Table 6 TABLE 6 Dispersant Pressure M_(a) Dry resistance PumpWeight Co- Weight (mole powder- After After 7 Humidity transport-Copolymer % polymer % %) n_(M) ing 1 day days resistance abilitycomparative product Comparative 100 — — 20.0 10.0 F — — — — product 1Comparative 100 — — 45.0 45.0 F — — — — product 3 Invented ProductsComparative 50 Invented 50 20.0 62.5 C E E E A product 1 product 7Comparative 45 Invented 55 31.3 75.3 C C C C A product 3 product 4

Example 5

[0144] 100 parts by weight of rapid-hardening Portland cement (TaiheiyoCement Corp.), 100 parts by weight of fine aggregate [siliceous sand (amixture of Nos. 3, 4 and 5, manufactured by Takeori Kogyo-sho)], 0.0025part by weight of a thickener [Metrose (Shin-Etsu Chemical Co., Ltd.)],0.02 part by weight of a retarder [sodium citrate (special grade)], 5parts by weight of an expansive material [Denka CSA (Denki KagakuKogyo)], 0.0015 part by weight of a foaming agent (metal aluminumpowder), the powdery dispersant in Table 8 and an anti-foaming agent[Foamlex 797 (Nicca Chemical Co., Ltd.)] in an amount shown in Table 7were mixed to produce a grout material. Water was added to the groutmaterial, and the mixture was kneaded for 3 minutes with a hand mixer togive slurry. This slurry was used in the following evaluation. Theresults are shown in Table 7.

[0145] Table 7 TABLE 7 Powdery dispersant Anti- Com- foaming Droppingtime (sec) pression agent Just Expan- Strength Co- weight Co- weight(weight M_(a) after After 30 After 60 After 90 sivity (N/ No. polymer %polymer % %) ({overscore (t)}/%) n_(M) kneading minutes minutes minutesBleeding ratio (%) mm²) 3-1 Invented 100 — — 0.3 20.0 84.6 5.6 8.1 10.613.8 less than 0.5 +0.82 57 product 5 3-2 Invented 100 — — — 20.0 84.65.8 8.3 11.0 13.9 less than 0.5 +0.83 51 product 5 3-3 Invented 30Invented 70 0.3 14.2 77.3 5.8 7.8 10.2 13.2 less than 0.5 +0.85 56product 10 product 2 3-4 Invented 100 — — 0.3 24.6 52.9 5.5 7.5 10.012.9 less than 0.5 +0.88 55 product 15 3-5 Invented 100 — — 0.3 34.070.6 5.2 7.0 9.6 11.5 less than 0.5 +0.89 53 product 18 3-6 compara- 100— — 0.3 61.0 101.0 7.2 10.8 17.0 18.8 less than 0.5 +0.81 51 tiveproduct

[0146] The weight-% of the anti-foaming agent is weight-% relative tothe total amount of the copolymer.

[0147] As shown in Table 7, when the powdery dispersant of the presentinvention is used in mortar grout, mortar grout excellent inflowability, bleeding ratio, expansivity and compression strength isobtained. In particular, when an anti-foaming agent is used, compressionstrength is stabilized. For use in mortar grout, Na salts (Nos. 3-1 to3-4) of copolymers derived from ester type monomers indicate a longerdropping time and more stable separation resistance than those of a Nasalt (No. 3-5) of a copolymer derived from ether type monomers. On theother hand, there is the case where the flowability of No. 3-6(Comparative Product) is deteriorated due to excessive thickening.

What is claimed is:
 1. A powdery dispersant for a hydraulic composition,which comprises at least one copolymer obtainable by polymerizing atleast one vinyl monomer (a) represented by the formula (1):

wherein R¹ and R² represent a hydrogen atom or a methyl group, R³represents a hydrogen atom or —COO(AO)_(n)X, m is a number of 0 to 2, pis a number of 0 or 1, AO represents a C₂₋₄ oxyalkylene group or anoxystyrene group, n is the average mole number and is a number of 2 to300 and X represents a hydrogen atom or a C₁₋₁₈ alkyl group; with atleast one vinyl monomer (b) represented by the formula (2):

wherein R⁴, R⁵ and R⁶ are the same as or different from one another andeach represent a hydrogen atom, a methyl group or —(CH₂)_(m1)COOM² inwhich —(CH₂)_(m1)COOM² may be combined with —COOM¹ or another—(CH₂)_(m1)COOM² to produce an anhydride, M¹ and M² of these groups notbeing present, M₁ and M₂ represent a hydrogen atom or a polyvalent metaland m, is a number of 0 to 2, in which the average mole number of C₂₋₄oxyalkylene groups or oxystyrene groups added to the dispersant moleculeis 45 to 150, (a)/[(a)+(b)]×100 ranges from 15 to 45 (mole %) and atleast part of the copolymer is a polyvalent metal salt.
 2. The powderydispersant according to claim 1, wherein (a)/[(a)+(b)]×100 ranges from20 to 35 mole %.
 3. A powdery dispersant for a hydraulic compositions,which comprises at least one copolymer obtained by polymerizing at leastone vinyl monomer (a) represented by the formula (1):

wherein R¹ and R² represent a hydrogen atom or a methyl group, R³represents a hydrogen atom or —COO(AO)_(n)X, m is a number of 0 to 2, pis a number of 0 or 1, AO represents a C₂₋₄ oxyalkylene group or anoxystyrene group, n is the average mole number of added groups and is anumber of 2 to 300 and X represents a hydrogen atom or a C₁₋₁₈ alkylgroup; with at least one vinyl monomer (b) represented by the formula(2):

 wherein R⁴, R⁵ and R⁶ are the same as or different from one another andeach represent a hydrogen atom, a methyl group or —(CH₂)_(m1)COOM² inwhich —(CH₂)_(m1)COOM² may be combined with —COOM¹ or another—(CH₂)_(m1)COOM² to produce an anhydride, M¹ and M² of these groups notbeing present, M₁ and M₂ represent a hydrogen atom or a monovalent metaland m, is a number of 0 to 2, in which the average mole number of C₂₋₄oxyalkylene groups or oxystyrene groups added to the dispersant moleculeis 50 to 150, (a)/[(a)+(b)]×100 ranges from 15 to 45 (mole %) and atleast part of the copolymers is a monovalent metal salt.
 4. The powderydispersant according to claim 3, wherein (a)/[(a)+(b)]×100 ranges from20 to 45 mole %.
 5. The powdery dispersant according to claim 1 or 3,wherein the average mole number of C₂₋₄ oxyalkylene groups or oxystyrenegroups added is 60 to
 130. 6. The powdery dispersant according to claim1 or 3, wherein the average mole number of C₂₋₄ oxyalkylene groups oroxystyrene groups added is 60 to
 115. 7. The powdery dispersantaccording to claim 1, wherein all the copolymers are polyvalent metalsalts in part.
 8. The powdery dispersant according to claim 1 or 3,which comprises a copolymer obtained from starting monomers containing98 to 100% by weight of the monomers (a) and (b).
 9. The powderydispersant according to claim 1 or 3, which comprises 50 to 100% byweight of dispersant particles whose diameter is 500 Mm or less.
 10. Ahydraulic composition comprising the powdery dispersant described inclaim 1 or 3 and a hydraulic composition.
 11. Use of the powderydispersant described in claim 1 or 3 as a dispersant for a hydrauliccomposition.
 12. A method of dispersing a hydraulic composition by thepowdery dispersant described in claim 1 or 3.